Tuning the hydrophilic/hydrophobic nanophase-separated morphology to enhance the conductivity is a considerable challenge in the field of anion exchange membranes (AEMs). Here, a series of novel aliphatic-aromatic copolymer AEMs were designed by embedding flexible alkyl chains of different lengths into rigid main chain of poly(ether sulfone). Compared to traditional aromatic polymer, the aliphatic-aromatic copolymers had more flexible main chains and longer hydrophobic segments, both of which promoted the nanophase separation and the formation of ionic clusters. Increasing aliphatic chain length made the ionic clusters larger and more interconnected, but too long aliphatic chain led to the formation of smaller ionic clusters because the ionic groups were far away from each other. An optimum length of the aliphatic chain (8 C) existed for the nanophase-separated morphology with the biggest ionic clusters (around 8 nm), with which the membrane showed the highest conductivity. A peak power density of 159 mW cm(-2) was obtained for the cell incorporating the 8 C membrane. Based on these, this study reveals a new direction to create a tunable nanophase-separated morphology for high-performance AEMs.